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By Pradeep K. Rohatgi, Clyde M. Adams

Dendritic aggregate of ice formed on freezing of aqueous soluitions has been studied. Chlorides of sodium, potassiutn, lithiunz , and hydroget1 were used as solutes. The spacing between ice platelets or den-drites was experimenlally found proportzonal to the square root of freezing time when the freezing rate was constant from beginrting to end of solidification; the constant freezing rates were obtained during freezing of small droplets of aqueous soliitions surrounded by relatively large heat sinks. The transverse growth velocity of the ice platelets is proportional to the square root of the freezing rate. During unidirectional freezing from a constant temperuture chill, the solution at each location is subjected to a spectrum of freezirtg rates. The freezing rate is ini- FREEZING of solutions has been a subject of investigation in many disciplines. Aqueous solutions offer the advantage of transparenty; their study is of special significance due to the increasing interest in freezing processes for desalination. In addition dendritic solidification of aqueous solutions is in many ways analogous to freezing of metallic solutions. Aqueous solutions of most ionic salts freeze with tially low, passes through a maximum, and then decreases until solidificatimz is complete. The den-drite spacing increases linearly with the distance from the chill surface; it is inversely profiortional to the square root of the maximum freezing rate. The dendrite spacings in the two systems (the constanl freezing rate and the varying freezing rate) are equal, when the maximum freezing rate of the varying freezing rate system equals the average freezing vale of the constant freezing rate system. Mass transport in interdendritic liquid duriug solidificatiotz is analyzed; the experimental observations indicate that maximum concentration difference (AC) and supercooling (AT) in the interdendritic liquid are indepexdent of freezing rate. the separation of practically pure ice crystals from the liquid phase; with very few exceptions there is no solid solubility of ionic salts in ice. As an ice crystal grows there is rejection of solute from the moving interface into the liquid. Since the rejected solute moves primarily by diffusion, concentration gradients are established in the liquid. The highest solute concentrations are found in liquid immediately adjacent to liquid-solid interfaces and lowest concentrations farthest from the interface. Two-phase equilibrium obtains only at the solid-liquid interface; at other locations the liquid becomes supercooled because temperature gradients are negligible compared to concentration gradients. This is an immediate consequence of the fact that thermal diffusivities are considerably higher than mass diffusivities.

Jan 1, 1968

By Amitava Gangulee, Michael B. Bever

The effects of changes in short-range order on some thermodynamic, electrical, and mechanical properties of the silver-rich Ag-Mg solid solutions have been investigated. The heats of formation at 273°K of several alloys after two different thermal treatments were measured by liquid metal solution calorimetry. Their electrical resistivities were measured at temperatures ranging from 4° to 773°k. Tensile tests and microhard-ness measurements were carried out at room temperature. An effective short-range order parameter and an effective interaction energy are defined. The measured changes in the properties are interpreted in terms of these quantities. The short-range order parameter is evaluated separately from calorimetric and X-ray data; the results are in fair agreement. Increasing short-range order lowers the resistivity of- the silver-rich Ag-Mg alloys but does not measurably affect the temperature dependence of the resistivity. Short-range order increases the yield stress of these alloys but does not affect the ultimate tensile stress. Changes in the effective short-range order parameter independently obtained from measured changes in the heat of formation, resistivity, and yield stress are in fair agreement. THE thermodynamic, electrical, and mechanical properties of solid solutions have been investigated as functions of composition in many alloy systems, but the effects of configurational variables, such as short-range or long-range order, on these properties have received much less attention. The silver-rich terminal solid solutions in the system Ag-Mg are well-suited for the investigation of the effects of order. The composition of these solid solutions may be varied over a range extending to about 27 at. pct Mg.1 Appreciable short-range ordering is likely to take place in these solid solutions; the degree of short-range order can be varied by suitable thermal treatments. In the alloy Ag3Mg long-range ordering is possible.2 This paper is primarily concerned with the effects of short-range order on some thermodynamic, electrical, and mechanical properties of the silver-rich Ag-Mg solid solutions.-The long-range ordering transition is the subject of a concurrent paper.3 1) EXPERIMENTAL PROCEDURES 1.1) Preparation of Specimens. Ag-Mg alloys containing up to 26.4 at. pct Mg were prepared by melting 99.99 pct pure Ag (obtained from Baker Chemical Co.) and 99.99 pct pure Mg (obtained from Eastman Chemi- cal Co. or Johnson Mathey & Co.) in graphite crucibles under molten potassium chloride. The solidified ingots were homogenized at 823°K for 10 days in evacuated Vycor capsules. A surface layer 6 in. thick was then removed by machining. The ingots were swaged into rods (2.5 mm diam) which were drawn into wires (1.0 mm diam). The wire specimens were annealed at 773°K for 24 hr in vacuum and either quenched into iced brine or cooled to room temperature over a period of 15 days. The average grain diameter (obtained from the linear intercepts) was about 0.1 mm. 1.2) Calorimetry. The heats of formation of the alloys were measured in a tin solution calorimeter as the difference in the heat effects of alternate additions of samples of an alloy and the mechanical mixture of its component elements. The additions were made from 273°K to the bath at about 623°K. The heat effect on addition of the alloys was approximately 5.5 kcal per g-atom. The procedure and the method of calculation have been described.4 1.3) X-Ray Diffraction. Short-range order parameters of two alloys were calculated from diffuse scattering intensities,' obtained with briquettes made from powdered specimens. A GE-XRD 5 diffractometer with filtered copper radiation was used. The absolute intensities were based on calibrations with paraffin. 1.4) Resistivity Measurements. The electrical resistivities were measured by a potentiometric method in which the potential drop across the specimen was compared with that across a standard resistance. For measurements below room temperature, the specimens were immersed in liquid helium (4°K), liquid nitrogen (78°K), dry ice and trichloroethylene (195°K), or ice and water (273°K). Measurements above room temperature were made on specimens held in a furnace under helium or in vacuum. The resistivity measurements were reproducible to ±0.5 pct or less. 1.5) Mechanical Tests. Tensile tests were carried out at room temperature with a Tinius-Olsen XY elec-tromatic Universal testing machine. Wire specimens (nominal gage length 1 in.) were used. The strain was measured with an extensometer, which had a sensitivity of 4 x 10-5; the strain rate was 10-3 min-1. Microhard-ness measurements were made with a square-pyramid indenter and a 100-g load.11 2) RESULTS AND DISCUSSION All measurements were made on two parallel sets of specimens, one quenched and the other slowly cooled from 773°K. The reported values are the averages of at least three measurements. In the range of magnesium concentration substantially below that of the composition Ag3Mg, quenched alloys have less short-range order than slowly cooled alloys. As the magnesium concentration approaches that of Ag3Mg, slow cooling develops long-range order. Quenching sup-

Jan 1, 1969

By AIME AIME

I am happy to welcome you to the twenty-third conference of the National Open-Hearth Committee, and our joint conference with the Blast Furnace Committee, of the American Institute of Mining and Metallurgical Engineers. It is appropriate that, for our fifteenth year anniversary, we should meet in the hotel and the city where this Open-Hearth Committee was inaugurated in 1925. At that first meeting, only a handful of men from a number of steel companies met to discuss ways and means to start a movement to improve the practical and metallurgical technique of open-hearth operations among independent manufacturers, as the United States Steel Corporation had carried on for many years.

Jan 1, 1940

By W. A. Selvig

BY plotting fixed carbon against British thermal units of coals free from mineral matter, and ranging in rank from anthracite to lignite, it is found that the coals of higher rank, from anthracite to the higher rank of the high-volatile bituminous coals, inclusive, can be separated into groups according to their degree of metamorphism by reference to their fixed carbon. Such charts show also that the coals lower in rank can be best separated into groups with respect to B.t.u., especially when plotted on the moist basis, that is, coal containing its natural bed moisture. A tentative scheme for coal classification was presented at the October, 1932, meeting of the Technical Committee on Scientific Classification, of the American Standards Association Sectional Com-mittee on Coal Classification. This scheme was sponsored by Sub-committee IV on Tentative Classification of Coals, under the chairmanship of W. T. Thom, Jr. It proposed the grouping of coals according to rank by reference to fixed carbon and B.t.u., on the basis of coal containing its natural bed moisture but free from mineral matter. This scheme proposed classifying coals into four broad classes: (1) anthracitic, (2) bituminous, (3) subbituminous, (4) lignitic.. The anthracitic class was divided into three groups designated as meta-anthracite, normal anthracite, and semianthracite. The bituminous class also was divided into three groups, low volatile, medium volatile, and high volatile. The high-volatile group was further subdivided into four subgroups according to moisture content, as follows: (1) less than 5 per cent, (2) 5 to 10 per cent, (3) 10 to 15 per cent, and (4) 15 per cent and more. The subbituminous class was divided into two groups, group, 1 including subbituminous coals having calorific values of 10,500 B.t.u. or more, and group 2 including those with less than 10,500 B.t.u. , The lignitic class of coal was divided into two groups both below 8,000.B.t.u., the one group consisting of consolidated and the other of unconsolidated

Jan 1, 1934

By D. S. Flett, D. W. West

The solvent extraction of chromium 111 has been studied for the system Cr 111, H,SO., H,O/RNH/RNH., xylene, where the primary amine used was Primene JMT. Rate studies have shown that extremely long equilibrium times are required, ranging from 1 hr at 80°C to 20 days at room temperature. Heating the solution prior to extraction increases the rate of extraction. The variation in the amount of Cr 111 extracted is an inverse function of the acidity of the aqueous phase. Thus, the slow rates of extraction appear to be connected with the hydrolysis of the Cr I11 species. Extraction isotherms for the extraction of Cr 111 have been obtained for two sets of experimental conditions, namely at 60°C and for a heat-treated solution cooled to room temperature. The separation of Fe 111 from Cr 111 and Cr 111 from Cu 11 in sulfate solution by extraction with Primene JMT has been studied and shown to be feasible. A survey of the literature relating to the solvent extraction of chromium showed that, although many systems exist for extraction of Cr VI, only a very few reagents have been found to extract Cr 111. The extraction of Cr III by di-(2-ethyl hexyl) phosphoric acid has been reported by Kimura.' A straight-line dependence of slope —2 was observed between log D,, and the log mineral acid concentration at constant extractant concentration. Since the slope of this plot reflects the charge on the ion extracted, it must be concluded that a hydrolyzed species of Cr III is being extracted. Carboxylic acids generally do not form extractable complexes with Cr III but di-isopropyl salicylic acie does extract Cr 111. Simple acid backwashing of the organic phase, however, failed to remove the chromium. Similar difficulty in backwashing was found by Hellwege and Schweitzer8 in the extraction of Cr I11 with acetyl-acetone in chloroform. The extraction of Cr 111 from chloride solutions by alkyl amines has been reported4-' but the maximum amount of extraction achieved in these studies did not exceed 10%: From sulfate solutions, however, Ishimori" has shown that appreciable amounts of Cr I11 were extracted by amines. The amines used were tri-iso-octyl amine, Amberlite LA-1 (a secondary amine, Rohm & Haas) and Primene JMT (primary amine, Rohm & Haas). The efficiency of extraction with regard to amine type was primary>secondary> tertiary. Appreciable extraction of Cr I11 was recorded for Primene JMT as the aqueous phase acidity tended to zero. The major difficulty with Cr I11 in solvent extraction systems stems from the nonlabile nature of the ion in complex formation. This accounts for the slow rate of extraction generally experienced and the difficulty encountered in backwashing the Cr I11 from the organic phase in the case of liquid cation exchangers. Consequently, the possibility of extraction of Cr I11 as a complex anion is attractive since the backwashing problems should be minimized in this way. From published data, it appeared that the extraction of chromium from sulfate solutions of low acidity by primary amines afforded the best chance of success for a useful solvent extraction system for Cr iii This paper presents the results of a study of the extraction of Cr I11 from sulfate solution by Primene JMT and examines the application of such an extraction procedure for the recovery of chromium from liquors containing iron and copper. Experimental Chromium solutions were prepared from chrome alum in sulfuric acid and sodium sulfate so as to maintain a constant concentration of sulfate ion of 1.5 molar. Solutions of Primene JMT were prepared in xylene and the amine equilibrated with sulfuric acid/sodium sul-fate solutions, of the same acidity as the chromium solution, until there was no change in acidity between the initial and final aqueous phases. The solutions of Primene JMT conditioned in this way were then used for the equilibration experiments. Equilibrations at 25°C were carried out in stoppered conical flasks shaken in a thermostat; equilibrations at all other temperatures were carried out in stirred flasks in a thermostat. After equilibration, the phases were separated and analyzed for chromium. In the tests on the rate of extraction, small samples of equal volume of both phases were withdrawn from time to time and the chromium distribution determined. The chromium analyses were carried out either coloi-imetrically using diphenyl carbazide, or volu-metrically using addition of excess standard ferrous ammonium sulfate and back titration of the excess iron with potassium dichromate. The oxidation of Cr 111 to Cr VI in the case of the raffinate solution was effected by boiling with potassium persulfate in the presence of silver nitrate and, for the backwash solution, by boiling with sodium hydroxide and hydrogen peroxide. Results Preliminary experiments indicated that extraction results were effected by the age of the chromium solution, higher distribution coefficients being obtained with solutions which had been allowed to stand for some time. Consequently a stock solution of chrome alum, 10 m moles per 1 Cr I11 in 1.4 M Na,SO,/O.l M &SO,,

Jan 1, 1971

By J. A. Brierley, Roshan B. Bhappu, D. H. Reynolds, P. H. Johnson

Although the economic importance of recovering copper by leaching of mine work dumps from open-pit operations has been realized for some time, serious attempts to understand and to improve such operations through scientifi research has been made only in recent years. This progress report covers the results of chemical, physical, and biological studies pertaining to the dump-leaching process and discusses salient features and parameters that may be helpful in improving such operations. The dump leaching of low-grade copper ores, as an integral part of the open-pit mining operations in the Southwest, has been practiced for the last 50 years and is increasing in importance as one of the major sources of copper. The recent acceleration in dump leaching can be attributed to: (1) the greater tonnages of low-grade ores mined and dumped at newer mines as well as resulting from increased stripping ratios at the older mines, (2) the relatively small investment required for dump leaching facilities per pound of copper recovered contrasted with expansion of milling facilities to recover equal amounts of the metal by raising tonnage throughout, (3) low labor requirements needed for leaching, and (4) the simple and continuous nature of the process needing little close supervision of trained operators. In the past, the mining companies have not worried about efficiency in dump leaching but have been satisfied with whatever metal recoveries could be made without much effort. However, because of the huge amounts of metal accumulating in the low-grade waste dumps, compared to the relatively small amount recovered annually, an operator today cannot leave dump leaching to chance. What appears to be a simple, empirical process is actually a very complex one involving a large number of critical factors that encompass Several Scientific disciplines, such as physics, chemistry, geology, biology, and hydrology. It is imperative that

Jan 1, 1970

By Howard C. Dunkle

Various factors can affect the quality of B1112 and B1113 steel as produced in a bessemer plant; among them: vessel-charging practice, blowing practice, ingot-pouring practice, ingot delivery-time practice, pit-heating practices, and ingot-rolling practice. Evaluation of the influence of ingot delivery time on quality has been chosen as the subject for this paper because this time is completely within the control of the operator, and on this particular factor there is a tremendous amount of information in the dusty archives of the average steel plant. In order to know how much improvement can be made and when attention should be directed to other factors that influence quality, in the continual struggle for improvement, the effect of ingot delivery time must be accurately evaluated. Once this is done, the importance of other variables can be accurately obtained, thus eliminating the necessity of resorting to opinions that are of doubtful value at best. In the study described herein, extensive use was made of the statistical card system as a method of determining the effect of ingot delivery time as a quality factor in bessemer screw-stock grades by simple direct correlation. The value of this statistical method as a means of accurately determining the influence of various factors has been amply demonstrated by Work1 for the bessemer process and by Hand and Gould2 and Fetters and Chipman3 for the open-hearth process. The quality records of 300,000 tons of bessemer screw-stock billets were used in this study of the effect of ingot delivery time on the rejections for breaks, pipe, check and seams. The reduction in the number of rejections for poor quality reduces the costs and increases the productivity per man-hour. The operator today, more than ever before, must know how to keep costs down, how to do it most quickly and in the best way, and how to obtain the highest quality in line with the ever increasing demands of the customer. It is necessary for him to know the individual relations and interrelations between various factors affecting the quality of the manufactured product if he is to produce material that will meet competitively the cost, performance, and quality demands of the trade. SIGNIFICANCE OF STEEL MANGANESE, MIXER SILICON AND STEEL SULPHUR AS QUALITY FACTORS In order to obtain the highest grade of material it is necessary to control many factors-not just one or two, as operators

Jan 1, 1945

By R. R. Byran, M. H. Kuryla

The Compania de Real del Monte y Pachuca started a 10-ton pilot plant in March, 1906. The distinctive features of the first cyanide installations at Pachuca were: grinding in cyanide solution, all-sliming and filtration of ore in which silver constituted the major value. Loreto started with a 300-ton " all-sliming" plant, using jaw crushers, grinding in stamps, Chilean mills and pebble mills in cyanide solution, concentrating with Wilfley tables and Johnson vanners, classification by cones and Dorr classifiers, intermittent thickening by decantation, mechanical agitation in flat tanks by stirrers and centrifugal pumps, filtration in Butters filters and precipitation by zinc shavings. The "San Francisco" mill No, 1 was contemporaneous, using a rather similar flow sheet. We shall trace the main developlnents in the three large mills of the district to their present practice. Developments in Large Mills of District Crushing and Grinding.—The trend of development in this part of the work has been the same as throughout the milling world; via., all increase in the degree of comminution of the ore in dry-crushing machines, the advance from pebble mill to rock mill and then to ball mill and the elimination of the stamp battery through the encroachment upon its field on the one side by finer dry crushing and on the other by more efficient wet grinding. The single-stage crushing in jaw type crushers, used at the start, has been replaced by two stages; at first, both stages by gyratory type and later the present practice, which is the same in all three mills, consisting of gyratory as primary followed by cone as secondary and delivering a product that may be rated at 56 to 1 inch. Primary wet grinding, at first performed by stamps and Chilean mills, is now by hall and/or rod mills; present practice differing widely in the three mills. Santa Gertrudis uses a 7 by 15 ft. rod mill, San Rafael

Jan 1, 1935

AlFred JamEs," London, Eug.:—I thank you, gentlemen, for Sour kind invitation to address you. It is a very great pleasure for me to be here at your annual meeting, and, although I have been a member since 1894, this is the first opportunity I have

Jan 1, 1909

By P. B. Leavenworth

Development in the Upper Texas Gulf Coast during 1945 resulted in the discovery of 23 new fields; one Miocene, eight Frio, three Cockfield-Yegua and eleven along the Wilcox trend. The Wilcox trend appears to he the most active at this time. Producing depths of the new Wilcox discoveries range from 2050 to 10,050 ft. Drilling along the Frio trend has been, for the greater part, projected to the deeper downdip sands. Eighteen of the new discoveries are classified as oil or condensate and five are gas discoveries.

Jan 1, 1946

By Allan B. Bowman

Several years ago a wealthy Chinese business friend of mine purchased an interest in a pro- posed oil well to be drilled a great distance from his home. A few months later it came in as a producer and proved to be a huge success and materially added to his resources. I asked him why a man of his wealth should be so lucky in a venture outside his sphere of knowledge when most people of modest means never seemed to get ahead. His answer was, "Fat Hoy takes a chance." Even though this was his answer, I knew from my association with him that there were other tempering considerations which Mr. Hoy applied before making up his mind to enter any transaction. First, he was a cautious individual. He was also a great believer in details and insisted on knowing everything possible about a situation, and finally, he was what we call a very solid individual with good basic instincts and judgment. This philosophy of Mr. Hoy may be applied to most any business but especially to those engaged in a search for natural resources such as mining where great risks are involved. This article concerns events in the history and growth of Banner Mining Co., with which I have been associated for 27 years in capacities from mine surveyor to vice president. Mr. Hoy's philosophy has played a significant role in the exploration projects of this company over the years, but what is more important, the officers, directors, and controlling interests in Banner have been aggressive in their search for ore reserves.

Jan 6, 1963

By N. Malakouti, R. H. Whipp, O. A. Kuby, R. M. Smailer

A detailed description of the development of the FIOR process (Brown, Campbell, and Saxon, 1966) and, subsequently, other technical papers related to the operation and start up of the FIOR plant (Violetta, 1975; Whipp, 1980) are available in the technical literature. The Fluidized Iron Ore Reduction (FIOR) process plant constructed in the Matanzas region of Venezuela represents the first commercial application of this technology. The FIOR process was developed by Exxon Co. during the 1950s and 1960s. The facility in Venezuela was designed and constructed by Davy McKee, with plant start-up in 1976. While there is a minority government ownership in the company, FIOR de Venezuela operates as a private sector company with the majority of ownership being private capital. The FIOR process is well suited to utilize the naturally occurring iron ore fines of the Cerro Bolivar and San Isidro iron ore deposits located less than 100 km (62 miles) south of the plant site. Availability of natural gas within 150 km (93 miles) to the north, and a location bordering on the confluence of the Caroni and the Orinoco Rivers makes for an ideal geographic site. Feed stock to the FIOR plant consists of naturally occurring iron ore fines from these ore bodies, which are screened to -6mm (-0.2 in.) prior to drying in the ore preparation plant. A simplified flow plan is shown in [Fig. 1]. The dried ore is then transferred to the top of a structure containing four fluid-bed reactors located above one another so the mineral may flow from one reactor to the next by gravity. A reducing gas containing 90% hydrogen is made by steam reforming of natural gas, a CO shift

Jan 1, 1983

By Howard C. Dunkle

Various factors can affect the quality of BIII2 and BIII3 steel as produced in a bessemer plant; among them: vessel-charging practice, blowing practice, ingot-pouring practice, ingot delivery-time practice, pit-heating practices, and ingot-rolling practice. Evaluation of the influence of ingot delivery time on quality has been chosen as the subject for this paper because this time is completely within the control of the operator, and on this particular factor there is a tremendous amount of information in the dusty archives of the average steel plant. In order to know how much improvement can be made and when attention should be directed to other factors that influence quality, in the continual struggle for improvement, the effect of ingot delivery time must be accurately evaluated. Once this is done, the importance of other variables can be accurately obtained, thus eliminating the necessity of resorting to opinions that are of doubtful value at best. In the study described herein, extensive use was made of the statistical card system as a method of determining the effect of ingot delivery time as a quality factor in bessemer screw-stock grades by simple direct correlation. The value of this statistical method as a means of accurately determining the influence of various factors has been amply demonstrated by Work1 for the bessemer process and by Hand and Gould2 and Fetters and Chipman3 for the open-hearth process. The quality records of 300,000 tons of bessemer screw-stock billets were used in this study of the effect of ingot delivery time on the rejections for breaks, pipe, check and seams. The reduction in the number of rejections for poor quality reduces the costs and increases the productivity per man-hour. The operator today, more than ever before, must know how to keep costs down, how to do it most quickly and in the best way, and how to obtain the highest quality in line with the ever increasing demands of the customer. It is necessary for him to know the individual relations and interrelations between various factors affecting the quality of the manufactured product if he is to produce material that will meet competitively the cost, performance, and quality demands of the trade. Significance of Steel Manganese, Mixer Silicon and Steel Sulphur as Quality Factors In order to obtain the highest grade of material it is necessary to control many factors—not just one or two, as operators

Jan 1, 1945

By Ronald A. Murdock

INTRODUCTION Exxon's Highland Uranium Operations in eastern Wyoming consists of an open pit, an underground mine and a mill complex. The geology of the deposit is reviewed in this paper, and an overview of the mining operations at both the surface and underground mines is presented. Topics discussed include geology, stripping of overburden and mining of ore in the open pit, and underground development and stoping methods. GEOLOGY The Highland uranium deposit was discovered in 1968 by Exxon Minerals Company, U.S.A., in Converse County, Wyoming, 35 miles north of Douglas. The mine is located at an elevation of about 5,200 ft in a high-plains, sagebrush-covered prairie typical of eastern Wyoming. The deposit is near the southern edge of the Powder River Basin in the Paleocene Fort Union Formation. The Fort Union Formation consists of 1,900 to 3,200 ft of sandstone, siltstone, mudstone, claystone and coal beds. Siltstone, mudstone and claystone are collectively referred to as "shale" at Highland. There are many alternating layers of shale and sandstone in the Fort Union Formation; but in the Highland area, there are only three principal sandstones, known as the Highland Sand Group, which host the uranium. The combined sand thickness is about 150 ft.

Jan 1, 1983

By L. A. Roe, John Jan

Iodine is a soft, lustrous, grayish-black nonmetallic element with a density of 4.9. It is the least active of the four members of the halogen family. The other members are, in order of increasing activity, bromine, chlorine, and fluorine. Iodine is a solid at ordinary temperatures, while bromine is a liquid and chlorine and fluorine are gases. Iodine melts at 113°C and volatilizes at 184.4°C to a blue-violet gas with an irritating odor. It occurs in nature only as iodates and iodides or other combined forms. It was discovered by Bernard Courtois in France in 1811, who noticed its presence as an unknown substance in crude soda ash obtained from burning seaweed. Gay-Lussac recognized it as a new element and named it iode, from the Greek word "ioeides or iodes" for violet color (MacMillan, 1970). The world production is not known with any great certainty, but it is probably between 25 and 35 million lb per year, of which about 30% is consumed in the United States. Geology and Mineralogy Iodine compounds occur as a minor constituent as a mineral in the Chilean nitrate deposits and in solution in brines and seawater. According to the US Geological Survey, it is the 47th most abundant element in the earth's crust. The minerals lautarite, Ca (I03)3 (calcium iodate), and dietzeite, Cat (103)2 (CrO4), (calcium iodate-chromate) are found in Chilean nitrate deposits which are located in Antofagasta and Tarapaca provinces on the eastern slope of the coast range in a desert area. Various brines contain iodine compounds. Seawater contains about 0.05 ppm of iodine and some seaweeds will extract and accumulate it up to 0.45% on a dry basis. Some coals in West Germany also contain iodine compounds. The known and potential sources of iodine reported in 1968 are given in Table 1. Table 2 lists estimated world iodine reserves. Iodine has been recovered from brines in Java, Indonesia, France, England, and the USSR. Iodine has also been recovered from seaweed in Ireland, Scotland, France, Japan, Norway, and the USSR. The indicated reserves and future resources of iodine are large but have never been adequately measured. Analysis Iodine as the free element can be detected by the characteristic blue color it gives to a starch solution. Quantitatively it is determined as the free element by titration with standard thiosulfate solutions using starch as an indicator. Colorimetric methods are also applicable. Markets and Prices Iodine and its compounds are generally marketed in the form of: iodine, crude; iodine, resublimed; calcium iodates; calcium iodide; potassium iodide, sodium iodide, and numerous organic compounds. Product Specifications Crude iodine, World market: 99-99.5% 12. Crude iodine, US produced, average: 99.8% 12. Crude iodine, USP XVII Specs: not less than 99.8% percent I2. Resublimed iodine is usually 99.9% and ACS specifications call for not over 0.005% total bromine and 0.020% nonvolatile materials (Anon., 1971). Prices, c.i.f. United States, for iodine have been steadily increasing from $1.18 per lb of crude in 1967 to $6.37-7.27 in January 1981 (Anon., 1981). In 1980 the price of iodine increased by 50%.

Jan 1, 1983

By H. [Eyring], B. J. Zwolinski

[ ] The authors are to be commended for their excellent work on the activities of components in the solid state. It is, however, felt that certain points require clarification with reference to diffusion in the solid state. It is a well established point that any rate process in a non-ideal system can be expressed by the general equation [ ] where ko is the specific rate in an ideal system, and ?A, ?B ... , the activity coefficients of the reactants and ?± and ?M,?N the activity coefficient of the activated complex and the intermediates, respectively. With reference to diffusion, the following simplified treatment in correcting for non-ideality is proposed. The same free energy change is involved in moving a particle from a solution of one activity to a solution of another activity,

Jan 1, 1947

By Rex B. McLellan

A simple model for dilute interslitial solid solutions is set up which enables a solubility equation for the equilibrium between the solid solution and the gaseous solute to be deduced. This solubility equation is used to estimate the partial thermody -namic functions of Ag-O and Fe-N dilute interstitial solid solutions from the measured equilibrium between these solutions and the gas phase. It is shown that the partial excess entropy of the solute atom in solution is a vibrational entropy which is due Principally to the oscillation of the interstitial atom and does not arise from electronic or elastic interaction between the solute atoms and solvent matrix. In this work measurements of the equilibrium between dilute solid interstitial solutions and a gaseous phase are used to deduce the important thermody-namic functions of the solid solution with the aid of a theoretical solubility equation formulated from a knowledge of the thermodynamic functions of the gas and a simple model for the solid solution. The quantity of principal interest which is deduced from the equilibrium data is the change in vibrational entropy occurring when a solute atom (u) is placed in an interstial site in the solvent (u) lattice. This paper forms part of a more general study in which the properties of condensed phases are deduced from measurements of the equilibrium between the condensed phase and a gas. Previous investigations have dealt with the equilibrium between krypton and liquid metals,' a pure metal and its vapor,' and dilute substitutional alloys and the vapor,3 and the subject has been popularly reviewed by McLellan.4 In the latter investigation3 the vapor pressures of very dilute Cu-Ag and Cu-Au alloys were measured with a Knudsen cell technique over a large range of temperatures and the analysis of the vapor-pressure data showed that the relative partial excess entropies were large and positive [ds= -Sudk = 30 for Au-Ag alloys and 150 for Cu-Au alloys; these values should be compared to unity, the value assumed for these exponentials in the quasi-chemical theory of solutions]. For many interstitial solutions experimental data is available for the equilibrium between the solution and a gaseous phase, and this can be used to deduce the vibrational entropies of the solute atoms in solution. The general method employed is to calculate the chemical potential of the solute atoms in the gas and equate this to pi, the chemical potential of solute atoms in the solid, which is deduced from a simple model set up for the dilute interstitial solution (in which the solute atoms act as bound oscillators in interstitial sites). This enables a theoretical solubility equation to be set up. In the case of Ag-O and Fe-N solid solutions the solubility c, is found to vary with temperature according to a relation of the type, where PU2 is the pressure of the O2 or Np molecules. Essentially, the theoretical solubility equation enables the parameter A(T), which gives the vibration entropy, and the parameter AH, which gives the energy of solution of a solute atom, to be estimated from the measured variation of solubility with temperature. The solutions treated are dilute enough to enable solute-solute interactions to be neglected so that the partial energy and excess entropy of solution E, and GS are not functions of composition and the configurational entropy is that of a random solution. Large positive values have been found for sxSu this quantity has not been given sufficient consideration in recent work on interstitial solutions and it is felt that the partial thermodynamic quantities of very dilute solutions should be understood before the thermodynamics of concentrated solutions can be fully appreciated. EXPERIMENTAL DATA 1) The Silver-Oxygen System. The measurements of Steacie and Johnson,= using silver foils, indicate that there is a pronounced minimum in the solubility vs temperature curve for O-Ag solutions. Eichenauer and Miiller6 have recently redetermined the solubility of oxygen in silver using a method developed in the investigation of metal-hydrogen systems.7 The solubility determinations were carried out on compact specimens of differing shapes and sizes and the results indicate a much lower solubility than was obtained by Steacie and Johnson with no minimum at 400°C. Subsidiary experiments showed that the erroneous results of Steacie and

Jan 1, 1964

By T. B. Counselman

WHEN one thinks of Minnesota iron ore, one thinks of big open pits, where high- grade ore is simply scooped up with a power shovel, loaded into cars, and hauled away for shipment to the blast furnace. On the western end of the Mesabi range, however, are large tonnages of iron ore which contain too much silica to be used directly in the blast furnace, and these ores must first be concentrated to a purer form. The Mesabi range is about 100 miles long and a maximum of 3 miles wide. The iron formation, which in its unaltered form is called taconite: consists of a banded iron- bearing chert. Where the high-grade ore bodies occur, these have resulted from folding and cracking with sub- sequent leaching out of the silica, leaving the iron oxide behind. The big open pits and the underground mines are situated in these concentrations.

Jan 1, 1941

By Alfred L. Beebe

to. A strip of thin platinum foil, about one inch square, is perforated with pin-holes over its entire surface. It is then bent into the shape of a letter U, and its opposite corners are connected by short pieces of platinum wire, so as to form a sort of basket. In this is placed a piece of amalgamated zinc of convenient size, and the whole is suspended by a stout platinum or silver wire in the bottle containing the solution to be reduced. Another strip of platinum foil,

Jan 1, 1886

By N. A. D. Parlee, M. M. A. El-Naggar, G. 8. Horsley

The apparatus was of a modified Sieverts type1&apos;2 with a reaction tube designed to function also as the cell component of an oxygen pressure gage. The reaction tube assembly is shown in Fig. 1 and described in Table I. The main body is a 1-in.-OD 15 mol pct calcia-stabilized zirconia tube. The ground-glass joint, g, the male part of which carried a prism for optical pyrometer use, was connected to the remainder of the Sieverts apparatus. The calibration of the cell (at its 1000°K operating temperature) for internal oxygen pressures (PO2in) in the range 0.2 to 10 9 atm was made against internal air pressures measured by mercury manometer and McLeod gage. At very low po2in values down to l<Tn atm the performance was checked by comparing pQ calculated from electromotive force measurement when the apparatus was filled with a) pure CO gas and b) a CO-CO2 mixture of the ratio CO-CO2 = 1:0.398, with Po, values calculated from the equilibrium constants of the following reactions at 1000°K:

Jan 1, 1968